Process of desulfurizing oils or distillates.



UNITED STATES ?atented December 22, 1903.

PATENT I OFFICE.

OTTO P. AMEND, OF NEW YORK, Y., ASSIGNOR OF ONE-HALF TO JOSIAH H. MAOY,OF BOONTON, NEW JERSEY.

PROCESS OF DESULFURIZING OILS OR DISTILLATES.

SPECIFICATION forming part of Letters Patent No. 747,348, dated December22, 1903.

Application filed March 10, 1903. Serial No. 147,061. (No specimens.)

To all whom it may concern:

Beit known that I, OTTO P. AMEND, acitizen of the United States,residingat New York, in the county of New York and State of New York, haveinvented new and useful Improvements in Processes of Desnlfurizing Oilsor Distillates, of which the following is a specification.

My invention relates to the elimination of sulfur from sulfur-bearingoil or distillates.

I have found that freshly-precipitated carbonate of copper will combinein neutral and alkaline solutions with sulfur and the sulfur compoundsfound in Ohio, Indiana, Texas, California, and Canada oils anddistillates and that upon efiecting such combination and removing thesaline solution the remaining hydrosulfid of copper may be eliminated byfirst subjecting it to the action of sulfuric acid, then removing thesludge and washing with water, after which the desulfurized distillatemay be treated by the usual acid and alkali treatment. This especiallyapplies to the naphthas and burning-oil distillates. The heavierdistillates, or those used in the manufacture of lubricating-oils, maybe desulfurized in the same manner; but as acid and alkali are seriouslyobjectionable in lubricating-oils that part is dispensed with in thetreatment of such oils, and a substitution is made immediately after theremoval of the saline copper solution by the employment of a ferroussulfate solution, which acts as a conveyor of oxygen. This exposed to acurrent of air or a jet of steam, or to both, eflects the oxidation ofany hydrosulfid of copper present and converts the same into a sulfate,which may be drawn ofi and separated .from the oil or distillate, andthereafter no sulfur reaction will occur, as may be demonstrated bytests made with plumbate of soda,mercury, sodium nitroprusside, or anyof the reagents employed to indicate sulfur reaction.

In carrying out my process I proceed as follows: I first wash thedistillate and blow it well with air, steam, or with both to remove asmuch sulfureted hydrogen as possible. I then remove the wash-water andadd of caustic-soda solution about one per cent. of the weight of thedistillate treated and containing from three to five per cent. of

its weight of caustic soda. I then agitate thoroughly. The causticsolution so applied removes a little of the sulfur of the lighter sulfurcompounds, as well as a quantity of organic acid, which is always foundin the distillate. After sufiicient agitation and settling the alkali isremoved for the double purpose of disposing of the coloring-matter,which it invariably takes up, and the refuse of the organic acids, whichit neutralizes. I then apply of an aqueous solution of a soluble salt ofcopper in weight about five per cent. of the weight of the distillateand of 25 Baum strength. The sulfate being the cheapest, I invariablyuse it for the purpose. After agitation I add of a saturated carbonateof potash or soda solution in weight about one per cent. of the weightof the distillate and of 25 Baum strength and agitate again.

acid and alkali treatment.

The remaining or heavy distillate obtained after the illuminating-oildistillate, which is used in the manufacture of lubricating-oils, istreated in the same manner, excepting the acid and acid and alkalitreatment are dispensed with, and immediately after the removal of theexcess of the carbonate of copper the distillate is exposed to theaction of a ferrous sulfate solution which acts as a conveyer of oxygen.This exposed to a current of air or jet of steam or both air and steameffects the oxidation of any hyd rosulfid of copper present and convertsthe same into a sulfate, which is then removed. The oil is then washedand allowed to settle and will prove upon test to be free of sulfur.

Having described my invention, what I claim as new, and desire to secureby Letters Patent of the United States, is

1. The process of desulfurizing oil or distillate which consists: ineliminating sulfureted hydrogen therefrom by washing, blowing withsteam. or air or by both steam and air; in removing fatty and organicacids contained therein by subjecting them to the action of an alkali,in removing the alkali after agitation; in agitating the oil ordistillate with a soluble salt of copper in the presence of a solublecarbonate; in removing the excess of copper salts and copperhydrosulfids thus formed and subjecting the oil or distillate to theaction of sulfuric acid, then removing the acid sludge, substantially asdescribed.

2. The process of desulfurizing oil or distillate which consists: inremoving fatty and organic acids contained therein by exposing saidacids to the action of an alkali; in agitating the oil or distillate andalkali and subsequently removing the alkali; in exposing the oil ordistillate to the action of a soluble salt of copper in the presence ofa soluble carbonate; in removing the excess of copper salts and copperhydrosulfids thus formed and subjecting the oil or distillate to theaction of sulfuric acid and then removing the sludge, substantially asdescribed.

3. The process of desulfurizing oil or distillate which consists: inremoving organic acids contained therein by subjecting them to theaction of an alkali; in agitating the oil or distillate and removing thealkali so used; in exposing the oil or distillate to the action of adissolved salt of copper in the presence of a soluble carbonate; inremoving the excess of copper salts and copper hydrosulfids thus formedand subjecting the oil or distillate to the action of sulfuric acid andthen removing the sludge, substantially as described.

4. The process of desulfurizing oil or distillate which consists: insubjecting the fatty or organic acids contained therein to the action ofan alkali and removing the alkali; in exposing the oil or distillate tothe action of a soluble salt of copper in the presence of a solublecarbonate; and removing the excess of copper salts, and the copperhydrosulfids thus formed, substantially as described.

5. The process of desulfurizing oil or distillate which consists: inexposing the oil or distillate to the action of a soluble salt of copperin the presence of a soluble carbonate; in removing the excess of coppersalts and the copper hydrosulfids thus formed; in subjecting the oil ordistillate to the action of sulfuric acid and then removing the sludgesubstantially as described.

6. The process of desulfurizing oil or distillate which consists; inexposing the oil or distillate to the'action of a soluble salt of copperin the presence of a soluble carbonate; in removing the excess of coppersalts and the copper hydrosulfids thus formed, substantially asdescribed.

7. The process of desulfurizing oil or distillate which consists; inexposing the oil or distillate to the action of a soluble salt of copperand subseqently to the action of a soluble carbonate, substantially asdescribed.

8. The process of desulfurizing oil or distillate which consists: inexposing the oil or distillate to the action of a freshly-precipitatedcarbonate of copper and, agitating it, substantially as described.

9. The process of desulfurizing oil or distillate which consists: inexposing the oil or distillate to the action of a soluble salt ofcopper; in exposing the oil or distillate to the action of a solublecarbonate and to contact with a saline solution (as ferrous-sulfatesolution), operating as a conveyor of oxygen; in removing the resultingcopper sulfate and washing the oil or distillate, substantially asdescribed.

10. The process of desulfurizing oil or distillate which consists: inexposing the sulfur and sulfur compounds therein contained to the actionof a soluble salt of copper, also to the action of a soluble carbonateand to contact with a saline solution containing ferrous sulfate and toa supply of air or steam or to both air and steam, substantially asdescribed. OTTO P. AMEND.

Witnesses:

JACOB B. TOCH, HERMANN T. MUELLER.

